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EP0548373A1 - Tole en acier revetue par une pellicule organique composite, presentant d'excellentes caracteristiques exterieures de brillant et d'action anti-rouille, ainsi que procede de fabrication - Google Patents

Tole en acier revetue par une pellicule organique composite, presentant d'excellentes caracteristiques exterieures de brillant et d'action anti-rouille, ainsi que procede de fabrication Download PDF

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Publication number
EP0548373A1
EP0548373A1 EP92914945A EP92914945A EP0548373A1 EP 0548373 A1 EP0548373 A1 EP 0548373A1 EP 92914945 A EP92914945 A EP 92914945A EP 92914945 A EP92914945 A EP 92914945A EP 0548373 A1 EP0548373 A1 EP 0548373A1
Authority
EP
European Patent Office
Prior art keywords
chromate
epoxy resin
coating
weight
steel sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP92914945A
Other languages
German (de)
English (en)
Other versions
EP0548373A4 (fr
EP0548373B1 (fr
Inventor
Takahiro Kubota
Masaaki Yamashita
Toyofumi Watanabe
Yoshio Kikuta
Kimio Kobori
Hideaki Ogata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Engineering Corp
Original Assignee
NKK Corp
Nippon Kokan Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP3197165A external-priority patent/JP2566857B2/ja
Priority claimed from JP3203547A external-priority patent/JP2568464B2/ja
Priority claimed from JP3203548A external-priority patent/JP2707168B2/ja
Application filed by NKK Corp, Nippon Kokan Ltd filed Critical NKK Corp
Publication of EP0548373A1 publication Critical patent/EP0548373A1/fr
Publication of EP0548373A4 publication Critical patent/EP0548373A4/fr
Application granted granted Critical
Publication of EP0548373B1 publication Critical patent/EP0548373B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/20—Chromatation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/60—Adding a layer before coating
    • B05D2350/65—Adding a layer before coating metal layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12542—More than one such component
    • Y10T428/12549—Adjacent to each other
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • Y10T428/12569—Synthetic resin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing component

Definitions

  • This invention relates to a coated steel sheet with a composite layer containing an organic substance, and having an excellent cosmetic corrosion resistance and excellent image clarity which is also excellent in anti-powdering property, weldability and paint adhesion, and which is beneficial for use in making automobile bodies, electric appliances, etc., and also to a process for manufacturing the same.
  • BACKGROUND ART The corrosion of automobile bodies by the salts which are sprinkled on road surfaces to prevent their freezing during the wintertime has become a big social problem recently in North America, northern Europe, and other countries or regions having a cold winter.
  • the use of a coated steel sheet having an improved corrosion resistance instead of a conventional cold rolled steel strip has, therefore, been increasing as one of the measures for improving the corrosion resistance of automobile bodies.
  • coated steel sheets are organic composite coated steel sheet, as disclosed in Japanese Patent Applications laid open under Nos. Sho 64-8033 and Hei 2-15177. These steel sheets comprise a steel sheet plated with zinc or a zinc alloy, and coated with a first layer formed by a chromate coating, and a second layer formed thereon by an organic coating composed of an organic resin which comprises a base resin obtained by adding one or more basic nitrogen atoms and two or more primary hydroxyl groups to the ends of molecules of an epoxy resin, a polyisocyanate compound and a blocked isocyanate compound, the organic resin film further containing specific proportions of silica and a sparingly soluble chromate. These strips are excellent in corrosion resistance, weldability, anti-powdering property and paint adhesion.
  • the recent inclination toward high-class and original automobiles has come to require a greater importance to be placed on the quality of a paint-finished body surface, particularly its image clarity.
  • the organic composite coated steel sheet as hereinabove described has, however, the drawback of being somewhat inferior to the conventional zinc or a zinc alloy plated steel sheet in image clarity as desired of the outer surface of the outer panel of the automobile body, though it may have a good perforation corrosion resistance as required of the inner surfaces of the outer and inner panels of the automobile body.
  • the known organic composite coated steel sheet cannot necessarily be said to be capable of forming a satisfactorily cosmetic corrosion resistance outer surface on the outer panel of the automobile body.
  • an object of this invention to provide an organic composite coated steel sheet which can form an excellent cosmetic corrosion resistance and image clarity on, for example, the outer surface of the outer panel of an automobile body, and a process for manufacturing the same.
  • the steel sheet of this invention having a composite coating containing an organic resin has as a first layer a chromate layer formed on the surface of a zinc or a zinc alloy plated steel sheet, and having a coating weight of 10 to 200 mg/m2 in terms of metallic chromium, and as a second layer formed on the first layer an organic resin film containing a blocked urethane-modified epoxy resin and a rust-preventing additive in a ratio of 90/10 to 40/60 (by weight), and having a thickness of 0.2 to 2 microns.
  • the basic composition of the blocked urethane-modified epoxy resin is as shown at i) below :
  • a modified epoxy resin obtained by adding a monoisocyanate, as well as a polyfunctional amine, to an epoxy resin enables the formation of a film having a still higher level of corrosion resistance.
  • the composition of the blocked urethane-modified epoxy resin is as shown at ii) below :
  • a modified epoxy resin obtained by adding phosphoric acid, as well as a polyfunctional amine, to an epoxy resin enables the formation of a film having a higher degree of adhesion to a steel strip, and an improved corrosion resistance.
  • the composition of the blocked urethane-modified epoxy resin is as shown at iii) below :
  • Silica or a sparingly soluble chromate is preferred as the rust-preventing additive in the film forming the second layer.
  • the process of this invention for manufacturing a steel sheet having a composite coating as hereinabove described comprises chromating the surface of a zinc or a zinc alloy plated steel sheet by coating it with a chromate solution and drying it without rinsing it with water to form a chromate layer having a coating weight of 10 to 200 mg/m2 in terms of metallic chromium on the strip surface, coating the chromate layer with a paint composition containing a blocked urethane-modified epoxy resin selected from among i) to iii) above and a rust-preventing additive in a ratio of 90/10 to 40/60 (by weight of non-volatile matter), and baking it to form an organic resin film having a thickness of 0.2 to 2 microns on the chromate layer.
  • Silica or a sparingly soluble chromate is preferably used as the rust-preventing additive to the paint composition.
  • a zinc or a zinc alloy plated steel sheet is used as a base material. It may, for example, be a steel sheet plated with zinc, a Zn-Ni alloy, a Zn-Fe alloy, a Zn-Mn alloy, a Zn-Al alloy, a Zn-Cr alloy or a Zn-Co-Cr alloy, or a steel sheet plated with a composite layer which contains one or more additives selected from among metal oxides, sparingly soluble chromate, polymers, etc. in a layer of zinc or a zinc alloy. It may also be a steel sheet coated with two or more plating layers of the same or different materials. The plating of the strip can be effected by any method selected from among electrodeposition, hot dipping and vapor-phase deposition on a case to case basis, though electrodeposition has an advantage over the other methods for plating a cold rolled steel strip.
  • the chromate layer formed on the surface of the steel sheet plated with zinc or a zinc alloy inhibits the corrosion of the steel sheet by its self-healing effect owing to hexavalent chromic acid ions. If the chromate layer has a coating weight of less than 10 mg/m2 in terms of metallic chromium, it cannot be expected to impart any satisfactory corrosion resistance to the steel sheet, and if its coating weight exceeds 200 mg/m2, it lowers the weldability of the steel sheet. Therefore, the chromate layer is so formed as to have a coating weight of 10 to 200 mg/m2 in terms of metallic chromium. Its coating weight is preferably from 20 to 100 mg/m2 in terms of metallic chromium to realize still higher levels of corrosion resistance and weldability.
  • any of the reacted-in-place, electrolytic and dried-in-place type of chromate coating can be employed for forming the chromate layer.
  • the dried-in-place type chromate is, however, preferred from the standpoint of corrosion resistance, since it can form a chromate layer containing a large amount of hexavalent chromic acid ions.
  • the dried-in-place type chromate is carried out by coating the steel sheet plated with zinc or a zinc alloy with a solution consisting mainly of a partially reduced aqueous solution of chromic acid, and further containing one or more additives selected from among (1) to (7) below, if required, and drying it without rinsing it with water :
  • a roll coater is usually employed for coating the strip with the solution for its chromate coating, though it is also possible to apply the solution to the strip by dipping or spraying and regulate its coating weight with an air knife, or by roll squeezing.
  • the organic resin film formed as the second layer on the chromate layer inhibits the excessive dissolution of hexavalent chromic acid ions from the chromate layer into a corrosive environment and thereby allows the chromate layer to produce a sustained effect of preventing corrosion, and the silica or chromate added to the organic resin film further improves the corrosion resistance of the steel sheet.
  • the organic resin film has a thickness which is smaller than 0.2 micron, no satisfactory corrosion resistance can be expected from the steel sheet, but if its thickness exceeds two microns, it lowers the weldability and image clarity of the steel sheet. Therefore, the organic resin film is formed with a thickness of 0.2 to 2 microns. Its thickness is preferably in the range of 0.3 to 1.5 microns to ensure that the strip have still higher levels of corrosion resistance, weldability and image clarity.
  • the organic resin film comprises a blocked urethane-modified epoxy resin and a rust-preventing additive.
  • the basic composition of the blocked urethane-modified epoxy resin is as shown at i) below :
  • a modified epoxy resin obtained by adding a monoisocyanate, as well as a polyfunctional amine, to an epoxy resin enables the formation of a film having a still higher level of corrosion resistance.
  • the composition of the blocked urethane-modified epoxy resin is as shown at ii) below :
  • a modified epoxy resin obtained by adding phosphoric acid, as well as a polyfunctional amine, to an epoxy resin enables the formation of a film having a higher level of adhesion to a steel sheet, and an improved corrosion resistance.
  • the composition of the blocked urethane-modified epoxy resin is as shown at iii) below :
  • the epoxy resin which can be employed for the purpose of this invention is, for example, an epoxy resin obtained as a glycidyl ether of bisphenol A or F, or a novolak ; or an epoxy resin obtained as a glycidyl ether by adding propylene or ethylene oxide to bisphenol A. It is also possible to use an aliphatic, alicyclic, or polyether-based epoxy resin. It is possible to use two or more epoxy resins together. It is preferable from the standpoint of corrosion resistance to use an epoxy resin having an epoxy equivalent of 400 or above.
  • the modified epoxy resin (A) can be obtained if the glycidyl group in the epoxy resin is reacted with a poly-functional amine.
  • the polyfunctional amine include : a primary alkanolamine such as ethanolamine, propanolamine, isopropanolamine or butanolamine ; a primary alkylamine such as propylamine, butylamine, octylamine or decylamine ; and a polyfunctional amine having two or more active hydrogen atoms in one molecule, such as ethylenediamine, diethylenetriamine, tetraethylenepentamine, xylenediamine, aminoethylpiperazine or norbornanediaminomethyl. It is possible to use two or more amines together. The use of an alkanolamine is preferred from the standpoints of corrosion resistance and paint adhesion.
  • the modified epoxy resin (A) can, for example, be produced by reacting at a temperature of 70°C to 150°C for 4 to 10 hours the epoxy resin and the polyfunctional amine which have been so mixed that the active hydrogen in the polyfunctional amine may have an equivalent which is from 1.1 to 1.8 times greater than that of the glycidyl group in the epoxy resin.
  • the modified epoxy resin (A) can also be prepared by reacting the glycidyl group in the epoxy resin with the polyfunctional amine, and reacting the reaction product thereof with a monoisocyanate compound.
  • the monoisocyanate compound can be obtained by reacting an aliphatic or aromatic monoamine with phosgene. It is also possible to use a product obtained by reacting one of the isocyanate groups in a diisocyanate compound with an aliphatic, aromatic or alicyclic alcohol. In this case, the use of an alcohol having four or more carbon atoms is preferred from the standpoint of its compatibility with the epoxy resin.
  • diisocyanate compound examples include : an aliphatic isocyanate compound such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate ; an aromatic isocyanate compound such as xylylene diisocyanate, 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate ; and an alicyclic isocyanate compound such as isophorone diisocyanate or norbornane diisocyanate methyl. It is possible to use two or more diisocyanates compound together. The modification of the epoxy resin with the monoisocyanate compound gives an improved corrosion resistance.
  • the modified epoxy resin (A) which comprises an epoxy resin, a polyfunctional amine and a monoisocyanate compound can, for example, be synthesized by reacting at a temperature of 70°C to 150°C for 4 to 10 hours the epoxy resin and polyfunctional amine which have been so mixed that the active hydrogen in the polyfunctional amine may have an equivalent which is from 1.1 to 1.8 times greater than that of the glycidyl group in the epoxy resin, adding the monoisocyanate so that it may have an equivalent which is from 0.7 to 2.0 times greater than that of the active hydrogen in the remaining amine, and continuing the reaction at a temperature of 30°C to 100°C.
  • the modified epoxy resin (A) can also be prepared by reacting the glycidyl group in an epoxy resin with a polyfunctional amine and a phosphoric acid.
  • the phosphoric acid which can be employed contains at least one P-OH group in a molecule, and may, for example, be orthophosphoric or pyrophosphoric acid, phosphorous acid, or polyphosphoric acid. It is also possible to use an ester of any such phosphoric acid, such as an alkyl or hydroxyalkyl ester thereof.
  • the modification of the epoxy resin with phosphoric acid enables an improved adhesion to a steel strip.
  • the modified epoxy resin (A) which comprises an epoxy resin, a polyfunctional amine and a phosphoric acid can, for example, be synthesized by reacting at a temperature of 70°C to 150°C for 4 to 10 hours the epoxy resin, polyfunctional amine and phosphoric acid which have been so mixed that the active hydrogen in the polyfunctional amine may have an equivalent which is 0.5 to 0.9 time greater than that of the glycidyl group in the epoxy resin, while the P-OH group in the phosphoric acid has an equivalent which is 0.1 to 0.5 time greater than that of the glycidyl group, or by reacting them stepwise.
  • the blocked urethane which is used for the purpose of this invention contains an appropriate compound which protects and renders inactive the highly active isocyanate group in an isocyanate compound, and the isocyanate group readily recovers its activity upon heating as a result of the dissociation of the blocking agent. It, therefore, serves as a curing agent for the modified epoxy resin.
  • the polyol which can be employed may, for example, be : a divalent alcohol such as ethylene glycol, propylene glycol, 1,6-hexanediol, diethylene glycol or triethylene glycol ; a trivalent alcohol such as glycerol or trimethylol-propane ; a low-molecular weight polyol such as pentaerythritol ; a polyester polyol which is polymerized from caprolactone or a low-molecular weight polyol, and dicarboxylic acid ; or a high-molecular weight polyol having a molecular weight of 400 or above, such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol.
  • a divalent alcohol such as ethylene glycol, propylene glycol, 1,6-hexanediol, diethylene glycol or triethylene glycol
  • a trivalent alcohol such as glycerol or trimethylol-propane
  • the polyisocyanate which can be employed may, for example, be : an aliphatic isocyanate compound such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate ; an aromatic isocyanate compound such as xylylene diisocyanate, 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate ; or an alicyclic isocyanate compound such as isophorone diisocyanate or norbornane diisocyanate methyl. It is also possible to use a mixture, or adduct thereof.
  • the blocking agent which can be employed may, for example, be : a compound of the phenol series, such as phenol ; a compound of the lactam series, such as ⁇ -caprolactam ; a compound of the oxime series, such as methyl ethyl ketooxime ; or a compound of the imine series, such as ethyleneimine. It is also possible to use a mixture of two or more such compounds.
  • the blocked isocyanate (B) can be obtained by reacting a mixture of polyisocyanate and polyol in which the polyisocyanate contains an excess of isocyanate group over the hydroxyl group in the polyol, whereby a prepolymer is produced, and protecting the isocyanate group remaining in the prepolymer with the blocking agent.
  • a react ion temperatuer of 30°C to 100°C is employed.
  • the blocked urethane-modified epoxy resin according to this invention can be obtained by mixing the modified epoxy resin (A) and the blocked urethane (B). They are mixed in an A/B ratio of 95/5 to 50/50 (by weight of nonvolatile matter). No A/B ratio exceeding 95/5 is desirable, as it results in an intermediate- or top-coat surface of lower clarity. No ratio that is smaller than 50/50 is desirable, either, as it results in a lower level of corrosion resistance.
  • the A/B ratio is preferably from 90/10 to 60/40 to achieve still higher levels of surface clarity and corrosion resistance.
  • An improved corrosion resistance can be achieved by adding silica and/or a sparingly soluble chromate to the blocked urethane-modified epoxy resin.
  • Silica promotes the formation, among other corrosion products of a zinc or a zinc alloy plated steel sheet, of basic zinc chloride which is an effective corrosion inhibitor. Moreover, silica apparently owes its corrosion-preventing effect to the fact that it is slightly soluble in a corrosive environment and forms a silicic acid ion which serves as a film-forming corrosion inhibitor. If the blocked urethane-modified epoxy resin and silica are employed in a ratio exceeding 90/10 by weight of nonvolatile matter, silica does not exhibit any satisfactory corrosion-preventing effect, but the film has a lower level of corrosion resistance.
  • the blocked urethane-modified epoxy resin fails to be an effective binder, and the film has a lower level of paint adhesion. Therefore, the blocked urethane-modified epoxy resin and silica are preferably employed in a ratio of 90/10 to 40/60 by weight of nonvolatile matter.
  • the silica which can be employed for the purpose of this invention may, for example, be : silica produced by a dry process (e.g. products of Nippon Aerosil Co., Ltd. known as AEROSIL 130, AEROSIL 200, AEROSIL 300,AEROSIL 380, AEROSIL R972, AEROSIL R811 and AEROSIL R805) ; organosilica sol (e.g. products of Nissan Chemical Industries, Ltd. known as MA-ST, IPA-ST, NBA-ST, IBA-ST, EG-ST, XBA-ST, ETC-ST and DMAC-ST) ; silica produced by a wet process of sedimentation (e.g. products of Tokuyama Soda Co., Ltd.
  • a dry process e.g. products of Nippon Aerosil Co., Ltd. known as AEROSIL 130, AEROSIL 200, AEROSIL 300,AEROSIL 380, AEROSIL R972, AEROSIL R8
  • T-32(S), K-41 and F-80) silica produced by a wet process of gelling
  • silica produced by a wet process of gelling
  • SYLOID 244, SYLOID 150, SYLOID 72, SYLOID 65 and SHIELDEX products of Fuji-Davison Chemical Ltd. known as SYLOID 244, SYLOID 150, SYLOID 72, SYLOID 65 and SHIELDEX. It is also possible to use a mixture of two or more types of silica.
  • the sparingly soluble chromate which is added to the organic film is considered to inhibit the corrosion of the steel sheet by discharging hexavalent chromic acid ions as a result of its slight dissolution in a corrosive ennvironment, as is the case with the chromate layer. If the blocked urethane-modified epoxy resin and the sparingly soluble chromate are employed in a ratio exceeding 90/10 by weight of nonvolatile matter, however, the sparingly soluble chromate does not exhibit any satisfactory corrosion-preventing effect, but the film has a lower level of corrosion resistance.
  • the blocked urethane-modified epoxy resin fails to be an effective binder, and the film has a lower level of paint adhesion. Therefore, the blocked urethane-modified epoxy resin and the sparingly soluble chromate are preferably employed in a ratio of 90/10 to 40/60 by weight of nonvolatile matter.
  • the sparingly soluble chromate which can be employed for the purpose of this invention is, for example, a fine powder of barium chromate (BaCrO4), strontium chromate (SrCrO4), calcium chromate (CaCrO4), zinc chromate (ZnCrO4 ⁇ 4Zn(OH)2), potassium zinc chromate (K2O ⁇ 4ZnO ⁇ 4CrO3 ⁇ 3H2O), or lead chromate (PbCrO4). It is also possible to use a mixture of two or more such salts.
  • barium or strontium chromate or both, since they can be expected to exhibit a self-healing effect by chromic acid ions over a long period of time.
  • the use of barium chromate which is poorly soluble in water is preferred to minimize the dissociation of water-soluble chromium from the organic film during the treatment of automobiles prior to paint application.
  • silica and a sparingly soluble chromate in specific proportions to the blocked urethane-modified epoxy resin enables the best corrosion resistance to be acheived by the combined corrosion-preventing effects thereof. More specifically, the best corrosion resistance can be obtained if silica and sparingly soluble chromate are employed in the following ratios by weight of nonvolatile matter :
  • silica and/or a sparingly soluble chromic acid salt is the principal additive to the blocked urethane-modified epoxy resin
  • a silane coupling agent e.g. an organic pigment of the condensed polycyclic type, or of the phthalocyanine series
  • a color dye e.g. an azo dye, or a dye composed of a complex salt of an azo dye and a metal
  • a lubricant e.g. polyethylene wax, fluororesin, graphite, or molybdenum disulfide
  • a rust-inhibitive pigment e.g.
  • aluminim dihydrogen tripolyphosphate aluminum phosphomolybdate, or zinc phosphate
  • an electrically conductive pigment e.g. iron phosphide, or antimony-doped tin oxide
  • a surface active agent e.g. aluminum phosphomolybdate, or zinc phosphate
  • a roll coater is usually employed for coating the strip with the paint composition as hereinabove described, though it is also possible to apply the composition by dipping or spraying and regulate its coating weight with an air knife, or by roll squeezing.
  • a hot-air, high-frequency induction, or infrared heating oven can, for example, be employed for heating the strip coated with the paint composition. It is heated to a temperature of from 50°C to 300°C, and preferably from 60°C to 250°C. If this invent ion is applied to a steel sheet with bake hardenability, it is preferably heated to a temperature not exceeding 150°C.
  • the steel strip of this invention usually has a layer of zinc or a zinc alloy, a chromate layer and an organic resin film on each side thereof
  • this invention covers also a strip having a layer of zinc or a zinc alloy, a chromate layer and an organic resin film formed only on one side thereof, while the other side thereof consists of a steel surface, a surface plated with zinc or a zinc alloy, or a surface plated with zinc or a zinc alloy and coated with a chromate layer.
  • Steel strips plated with zinc or zinc alloys were degreased with an alkali, rinsed with water, dried, given chromating treatment, and coated with paint compositions by a roll coater, followed by their baking, to prepare coated steel sheet for making automobile bodies.
  • the resulting steel sheets each coated with an organic composite coating were tested for corrosion resistance, image clarity, paint adhesion and weldability.
  • the conditions employed for their preparation were as follows :
  • a chromating solution having the composition shown below was applied by a roll coater, and dried without rinsing with water.
  • the coating weight of the chromate layer was controlled by varying the ratio in peripheral speed of the pickup and applicator rolls in the roll coater.
  • Chromic acid anhydride 20 g/l.
  • Phosphoric acid ion 4 g/l.
  • Zirconium fluoride ion 1 g/l.
  • Zinc ion 1 g/l.
  • Hexavalent chromium/trivalent chromium 3/3 (by weight).
  • Chromic acid anhydride/zirconium fluoride ion 20/l (by weight).
  • a bath containing 30 g of chromic acid anhydride and 0.2 g of sulfuric acid per liter and having a temperature of 40°C was used for cathode electrolysis at a current density of 10 A/dm2 to form a chromate layer on the strip, followed by rinsing with water, and drying.
  • the coating weight of the chromate layer was regulated by controling the amount of the electric current employed for the electrolysis.
  • a solution containing 30 g of chromic acid anhydride, 10 g of phosphoric acid, 0.5 g of NaF and 4 g of K2TiF6 per liter and having a temperature of 60°C was sprayed on the strip, followed by rinsing with water, and drying.
  • the coating weight of the chromate layer was control led by varying the length of time employed for the treatment.
  • the organic resins which were employed are shown in TABLES 2 to 4.
  • the modified epoxy resins (A1) to (A3) and blocked urethanes (B) appearing in the tables were prepared by the processes described below.
  • a reaction vessel equipped with a condenser, a stirrer and a thermometer was charged with 1200 parts of a bisphenol A epoxy resin having an epoxy equivalent of 2000, 800 parts of xylene and 1050 parts of cyclohexanone, and they were heated under stirring to form a solution. 36 parts of isopropanolamine was added, and reacted at 100°C for five hours to yield a modified epoxy resin A1 having a resin content of 40%.
  • a reaction vessel equipped with a condenser, a stirrer and a thermometer was charged with 500 parts of a bisphenol A epoxy resin having an epoxy equivalent of 1500, 385 parts of xylene and 385 parts of cyclohexanone, and they were heated under stirring to form a solution.
  • 20 parts of isopropanolamine was added, and reacted at 100°C for five hours, and 65 parts of monoisocyanate, which was an addition product of 2,4-tolylene diisocyanate having an NCO (isocyanate) percentage of 13% and octyl alcohol, was added for reaction at 60°C for five hours to yield a modified epoxy resin A2 having a resin content of 40%.
  • a reaction vessel equipped with a condenser, a stirrer and a thermometer was charged with 500 parts of a bisphenol A epoxy resin having an epoxy equivalent of 2500, 385 parts of xylene and 385 parts of cyclohexanone, and they were heated under stirring to form a solution.
  • Five parts of monoethanylamine was added, and 7.6 parts of dibutylphosphoric acid was also added, for reaction at 100°C for five hours to yield a modified epoxy resin A3 having a resin content of 40%.
  • a reaction vessel equipped with a condenser, a stirrer and a thermometer was charged with 440 parts of polyethylene glycol having a molecular weight of 1000 and 125 parts of xylene, and while they were heated at 60°C under stirring, 153 parts of 2,6-tolylene diisocyanate was added, whereby an intermediate having an NCO percentage of 4.8% was obtained. Then, 106 parts of ⁇ -caprolactam was added to continue the reaction, and after it had been ascertained that the reaction product had an NCO percentage of 0%, 175 parts of butanol was added, whereby a blocked urethane B1 having a resin content of 70% was obtained.
  • TABLES 7 to 18 show the details in construction of the coated steel strips prepared as hereinabove described, and the results of their evaluation for corrosion resistance (cosmetic corrosion resistance), image clarity, paint adhesion, and weldability. The evaluation for each property was made by the method described below.
  • Each test specimen was prepared by coating a cationic electrodeposition primer of U-600, product of Nippon Paint Co., Ltd., with a thickness of 25 microns, a sealer of KPX-36, product of Kansai Paint Co., Ltd., with a thickness of 30 microns, and a top coat of LUGA BAKE B-531, product of Kansai Paint Co., Ltd., with a thickness of 35 microns.
  • a cross cut was made in the specimen with a knife, and the specimen was given 300 or 400 cycles of a cyclic corrosion test, each cycle consisting of 10 minutes of a salt spray test, 155 minutes of drying, 75 minutes of a humidity cabinet test, 160 minutes of drying and 80 minutes of another humidity cabinet test.
  • the creepage width from the cross cut in each specimen was determined as a measure of its corrosion resistance (cosmetic corrosion resistance). The results of evaluation are shown by symbols each representing a certain range of width as indicated below :
  • An image clarity measuring instrument made by Suga Testing Machine Co., Ltd. was employed for forming an image through a 0.5 mm wide slit on each specimen having an cationic E-coat, a sealer and a top coat formed thereon as described at (a) above, and measuring the clarity C of the image.
  • the results are shown by symbols each representing a certain range of clarity as indicated below :
  • a continuous spot-welding test was made on each specimen by employing a CF electrode, a electrode force of 200 kgf, a weld time of 10 cycles/50 Hz, and a welding current of 10 kA, and the number of the spots which could be made continuously on the specimen was counted as a measure of its weldability.
  • the results are shown by symbols each representing a certain range of the number of spots as indicated below :
  • the coated steel sheet of this invention is useful as a material for automobiles and electric appliances for domestic use, since it has a surface which is excellent in cosmetic corrosion resistance and image clarity, as well as in paint adhesion and weldability.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

Tôle en acier revêtue par une pellicule organique composite, présentant d'excellentes caractéristiques d'action anti-rouille et de brillant quand on l'applique sur l'extérieur d'une carrosserie d'automobile. On la fabrique en revêtant la surface d'une tôle en acier galvanisée avec une couche de chromate à teneur donnée en chrome et en constituant sur ladite tôle une pellicule en résine organique, dont l'épaisseur se situe entre 0,2 et 2 mum, préparée au moyen de l'apport d'une proportion donnée d'un additif anti-rouille à une résine époxy modifiée à base d'uréthane en masse préparée au moyen de l'apport d'une proportion donnée d'un uréthane en masse comprenant un polyol, un polyisocyanate et un agent bloquant à une résine époxy modifiée comprenant une résine époxy, une amine polyfonctionnelle et, si nécessaire, un monoisocyanate ou un acide phosphorique.
EP92914945A 1991-07-11 1992-07-10 Tole en acier revetue par une pellicule organique composite, presentant d'excellentes caracteristiques exterieures de brillant et d'action anti-rouille, ainsi que procede de fabrication Expired - Lifetime EP0548373B1 (fr)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
JP197165/91 1991-07-11
JP3197165A JP2566857B2 (ja) 1991-07-11 1991-07-11 耐外面錆性および鮮映性に優れた有機複合被覆鋼板およびその製造方法
JP19716591 1991-07-11
JP203548/91 1991-07-19
JP20354891 1991-07-19
JP20354791 1991-07-19
JP3203547A JP2568464B2 (ja) 1991-07-19 1991-07-19 耐外面錆性および鮮映性に優れた有機複合被覆鋼板およびその製造方法
JP203547/91 1991-07-19
JP3203548A JP2707168B2 (ja) 1991-07-19 1991-07-19 耐外面錆性および鮮映性に優れた有機複合被覆鋼板およびその製造方法
PCT/JP1992/000891 WO1993001004A1 (fr) 1991-07-11 1992-07-10 Tole en acier revetue par une pellicule organique composite, presentant d'excellentes caracteristiques exterieures de brillant et d'action anti-rouille, ainsi que procede de fabrication

Publications (3)

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EP0548373A1 true EP0548373A1 (fr) 1993-06-30
EP0548373A4 EP0548373A4 (fr) 1994-03-17
EP0548373B1 EP0548373B1 (fr) 2000-01-05

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US (1) US5429880A (fr)
EP (1) EP0548373B1 (fr)
KR (1) KR0125011B1 (fr)
AU (1) AU2274792A (fr)
DE (1) DE69230523T2 (fr)
WO (1) WO1993001004A1 (fr)

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JP5335159B1 (ja) * 2012-04-25 2013-11-06 日新製鋼株式会社 黒色めっき鋼板の製造方法および黒色めっき鋼板の成形体の製造方法
JP6806488B2 (ja) * 2016-07-29 2021-01-06 株式会社Adeka 硬化性樹脂組成物、及び該組成物を用いた構造材料接合用接着剤
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Also Published As

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WO1993001004A1 (fr) 1993-01-21
DE69230523D1 (de) 2000-02-10
DE69230523T2 (de) 2000-06-29
KR930702083A (ko) 1993-09-08
EP0548373A4 (fr) 1994-03-17
KR0125011B1 (ko) 1997-11-27
US5429880A (en) 1995-07-04
AU2274792A (en) 1993-02-11
EP0548373B1 (fr) 2000-01-05

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